Expansive cement

ABSTRACT

An expansive additive composition for use in Portland cements and a method of using such an additive composition is provided. The additive composition can include a calcium aluminate cement additive and a lithium compound. The additive composition is capable of producing expansion in set cements when the temperature is at or below room temperature and minimizes the amount of calcium aluminate cement additive needed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.15/319,309 filed Dec. 15, 2016, now allowed, which is a national phaseof PCT Patent Application No. PCT/US2014/058270 filed Sep. 30, 2014, andwhich is incorporated by reference.

FIELD

This disclosure relates to cement compositions and more particularly toexpansive cement compositions, which expand slightly after setting. Suchcompositions are useful for cementing a casing in place in a bore of anoil, gas or other well and in well abandonment operations.

BACKGROUND

Cement systems, such as Portland cement, typically are subject toshrinkage during and after setting and hardening. In some applicationssuch shrinkage is problematic. For example, in downhole applications forcementing a casing in a well and for abandonment plugs in wells, it iscrucial that good bonding occurs between the set cement and the casingand/or between the set cement and the formation borehole wall in orderto achieve effective zonal isolation. Poor cement/formation bonding,poor cement/casing bonding, expansion and contraction of the casingresulting from internal pressure or thermal stress, and inadequate mudremoval all contribute to the formation of small gaps or “microannuli”at the cement/casing or cement/formation interface. These microannuliallow communication between the zones through which the wellboreextends.

Cement systems that expand slightly after setting are a proven means ofpreventing and/or sealing microannuli and improving primary cementingresults. The improved bonding is the result of mechanical resistance ortightening of the cement against the casing and formation. Inunrestrained environments, such as cement use in buildings and roads,expansion of the cement during setting and hardening can result incracking and failure. In the restrained downhole environment, the cementexpands to eliminate void spaces and reduce internal cement porosity.

Current additive compositions that are introduced into Portland cementsto provide expansive cement typically rely on elevated temperatures toachieve a sufficient expansion effect, often above 100° F. (37.8° C.).There is a need, however, for expansive Portland cement systems thatachieve sufficient expansion at temperatures below 100° F. (37.8° C.)and more typically at temperatures below room temperature (about 73° F.or about 23° C.).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a system for preparation and delivery of a cementcomposition to a wellbore in accordance with aspects of the presentdisclosure.

FIG. 2A illustrates surface equipment that may be used in placement of acement composition in a wellbore in accordance with aspects of thepresent disclosure.

FIG. 2B illustrates placement of a cement composition into a wellboreannulus in accordance with aspects of the present disclosure.

FIG. 3 is a graph of expansion versus days for each cement compositionsample in the Examples.

FIG. 4 is a chart of the expansion rate for each cement compositionsample in the Examples.

DETAILED DESCRIPTION

It has now been discovered that relatively small amounts of a lithiumcompound added to a Portland cement along with some calcium aluminatecement and calcium sulfate provide for cements having suitable expansioneven at relatively low temperatures, generally below about 100° F.(37.8° C.) and more typically below about room temperature (73° F. or23° C.) and even at temperatures below 60° F. (15.6° C.) or temperaturesof about 55° F. (12.8° C.) or below.

A typical expansive cement system or composition according to anembodiment comprises a Portland cement and an expansion additive. Whilemost Portland cements can be used, typically the Portland cement isselected from the group consisting of API Class A Portland cement, APIClass C Portland cement, API Class G Portland cement, API Class HPortland cement and any combination thereof. Additionally, the cementsystem can include fluid loss additives, set accelerators, cure rateadjusters, and similar.

The expansion additive composition comprises calcium aluminate cement, alithium compound and calcium sulfate (typically added as ground gypsum).The calcium sulfate can be added to the cement system separately fromthe other components of the expansion additive composition. Theexpansion additive composition can also comprise calcium hydroxide andsodium bicarbonate.

An exemplary expansion additive composition comprises calcium aluminatepresent from about 5% to about 50%; a lithium compound present fromabout 0.01% to about 5.00%, calcium sulfate present in an amount fromabout 50% to about 80% by weight of the composition; calcium hydroxidepresent in an amount from about 1% to about 20% by weight of thecomposition; and sodium bicarbonate present in an amount from about 0.1%to about 5% by weight of the composition, all based on weight of theexpansion additive composition.

Generally, the calcium aluminate cement can be present in an amount ofat least about 5%, at least about 10% or at least 15% up to about 50%,about 40% or 35% by weight of the additive composition. The lithiumcompound can be present in an amount of at least about 0.01%, at leastabout 0.05% or at least 0.10% up to about 5.00%, about 1.00%, 0.50% or0.30% by weight of the additive composition. The calcium sulfate can bepresent in an amount of at least about 40%, at least about 50%, or atleast 60% up to about 90%, about 80% or 75% by weight of the additivecomposition. The calcium hydroxide can be present in an amount from atleast about 1%, at least about 5% or at least 7% up to about 20%, about15% or 12% by weight of the additive composition. The sodium bicarbonatecan be present in an amount from at least about 0.1%, at least about0.5% or at least 1.0% up to about 5%, about 3% or 2% by weight of theadditive composition.

While not wishing to be bound by theory, the volume expansion of theresulting ettringite product from the calcium aluminate and calciumsulfate provides expansion action, and it is believed that the lithiumcompound co-additive enhances the performance of the expansion additivecomposition through interaction with the calcium aluminate cement. Theaddition of a lithium compound to the other components of the expansionadditive composition improves the reactivity of the system such that therate of expansion is more rapid and the desirable action of theexpansive cement composition can be utilized effectively at lowertemperatures than that of conventional expansion additives. The lithiumcompound can result in an expansion of at least 10% in the set cementwithin 1 day, of at least 15% in the set cement within 3 days and atleast 17% within 7 days. Exemplary lithium compounds are lithium salts.Most lithium salts can be used in the expansion additive composition.Suitable lithium salts include lithium carbonate, lithium halides,lithium sulfate, hydrates of lithium sulfate, lithium nitrate, andlithium hydroxide.

The above described expansion additive composition can be mixed withPortland cement to produce an expansive cement composition. Typically,the expansion additive composition will be added in an amount from about1% to about 20% based on the weight of the Portland cement. Moretypically, the expansion additive composition will be added in an amountfrom 5% to 15% based on the weight of the Portland cement. Prior to usedownhole, water is added to the resulting mixture to create a slurry.The water will typically be added in an amount from about 30% to about60%, and more typically, from 40% to 55% by weight of the Portlandcement.

Generally, the resulting expansive cement composition can comprise fromabout 0.5% to about 8.0% calcium aluminate cement by weight of thePortland cement. However, the expansive cement composition can compriseat least about 1.0%, or at least 1.5% up to about 5.0% or 3.5% calciumaluminate cement by weight of the Portland cement.

The expansive cement composition can comprise from about 0.001% to about0.500% lithium compound by weight of the Portland cement. However, theexpansive cement composition can comprise at least about 0.005%, or atleast 0.010% up to about 0.150, about 0.100% or 0.050% lithium compoundby weight of the Portland cement.

The expansive cement composition can comprise from about 1% to about 15%calcium sulfate by weight of the Portland cement. However, the expansivecement composition can comprise at least about 5% up to about 10%calcium sulfate by weight of the Portland cement. Further, the calciumhydroxide can be present in an amount from about 0.1% to about 3.0% orfrom 0.5% to 2.0% by weight of the Portland cement and the sodiumbicarbonate can be present in amount from about 0.01% to about 1.00% orfrom 0.05% to 0.5% by weight of the Portland cement.

In some embodiments, the expansive cement composition comprises a setaccelerator, such as calcium chloride. If calcium chloride is used, itcan be present in an amount of at least about 0.1% or about 0.5% up toabout 5.0% or up to 2% by weight of the Portland cement. Additionally,the set accelerator can be mixed with the expansion additive compositionprior to the additive composition being introduced to the Portlandcement.

The expansive cement composition can be used in a method wherein thePortland cement, expansion additive composition and water are mixed toform a slurry. The resulting cement slurry composition is thenintroduced into the bore to form a plug or to cement casing in theborehole. In cementing casing in the borehole, the cement slurrycomposition is placed between the casing and the borehole wall. Theborehole can be below about 100° F. (37.8° C.), below 73° F. (23° C.),below 60° F. (15.6° C.) or at about 55° F. (12.8° C.) or below at thesite to be cemented.

The exemplary compositions disclosed herein may directly or indirectlyaffect one or more components or pieces of equipment associated with thepreparation, delivery, recapture, recycling, reuse, and/or disposal ofthe disclosed compositions. For example, the disclosed compositions maydirectly or indirectly affect one or more mixers, related mixingequipment, mud pits, storage facilities or units, compositionseparators, heat exchangers, sensors, gauges, pumps, compressors, andthe like used to generate, store, monitor, regulate, and/or reconditionthe exemplary compositions. The disclosed compositions may also directlyor indirectly affect any transport or delivery equipment used to conveythe compositions to a well site or downhole such as, for example, anytransport vessels, conduits, pipelines, trucks, tubulars, and/or pipesused to compositionally move the exemplary compositions from onelocation to another, any pumps, compressors, or motors (e.g., topside ordownhole) used to drive the exemplary compositions into motion, anyvalves or related joints used to regulate the pressure or flow rate ofthe exemplary compositions, and any sensors (i.e., pressure andtemperature), gauges, and/or combinations thereof, and the like. Thedisclosed compositions may also directly or indirectly affect thevarious downhole equipment and tools that may come into contact with thecement compositions/additives such as, but not limited to, wellborecasing, wellbore liner, completion string, insert strings, drill string,coiled tubing, slickline, wireline, drill pipe, drill collars, mudmotors, downhole motors and/or pumps, cement pumps, surface-mountedmotors and/or pumps, centralizers, turbolizers, scratchers, floats(e.g., shoes, collars, valves, etc.), logging tools and relatedtelemetry equipment, actuators (e.g., electromechanical devices,hydromechanical devices, etc.), sliding sleeves, production sleeves,plugs, screens, filters, flow control devices (e.g., inflow controldevices, autonomous inflow control devices, outflow control devices,etc.), couplings (e.g., electro-hydraulic wet connect, dry connect,inductive coupler, etc.), control lines (e.g., electrical, fiber optic,hydraulic, etc.), surveillance lines, drill bits and reamers, sensors ordistributed sensors, downhole heat exchangers, valves and correspondingactuation devices, tool seals, packers, cement plugs, bridge plugs, andother wellbore isolation devices, or components, and the like.

Referring now to FIG. 1, a system that may be used in the preparation ofa cement composition in accordance with example embodiments will now bedescribed. FIG. 1 illustrates a system 2 for preparation of a cementcomposition and delivery to a wellbore in accordance with certainembodiments. As shown, the cement composition may be mixed in mixingequipment 4, such as a jet mixer, re-circulating mixer, or a batchmixer, for example, and then pumped via pumping equipment 6 to thewellbore. In some embodiments, the mixing equipment 4 and the pumpingequipment 6 may be disposed on one or more cement trucks as will beapparent to those of ordinary skill in the art. In some embodiments, ajet mixer may be used, for example, to continuously mix the composition,including water, as it is being pumped to the wellbore.

An example technique and system for placing a cement composition into asubterranean formation will now be described with reference to FIGS. 2Aand 2B. FIG. 2A illustrates surface equipment 10 that may be used inplacement of a cement composition in accordance with certainembodiments. It should be noted that while FIG. 2A generally depicts aland-based operation, those skilled in the art will readily recognizethat the principles described herein are equally applicable to subseaoperations that employ floating or sea-based platforms and rigs, withoutdeparting from the scope of the disclosure. As illustrated by FIG. 2A,the surface equipment 10 may include a cementing unit 12, which mayinclude one or more cement trucks. The cementing unit 12 may includemixing equipment 4 and pumping equipment 6 (e.g., FIG. 1) as will beapparent to those of ordinary skill in the art. The cementing unit 12may pump a cement composition 14 through a feed pipe 16 and to acementing head 18 which conveys the cement composition 14 downhole.

Turning now to FIG. 2B, the cement composition 14 may be placed into asubterranean formation 20 in accordance with example embodiments. Asillustrated, a wellbore 22 may be drilled into the subterraneanformation 20. While wellbore 22 is shown extending generally verticallyinto the subterranean formation 20, the principles described herein arealso applicable to wellbores that extend at an angle through thesubterranean formation 20, such as horizontal and slanted wellbores. Asillustrated, the wellbore 22 comprises walls 24. In the illustratedembodiments, a surface casing 26 has been inserted into the wellbore 22.The surface casing 26 may be cemented to the walls 24 of the wellbore 22by cement sheath 28. In the illustrated embodiment, one or moreadditional conduits (e.g., intermediate casing, production casing,liners, etc.) shown here as casing 30 may also be disposed in thewellbore 22. As illustrated, there is a wellbore annulus 32 formedbetween the casing 30 and the walls 24 of the wellbore 22 and/or thesurface casing 26. One or more centralizers 34 may be attached to thecasing 30, for example, to centralize the casing 30 in the wellbore 22prior to and during the cementing operation.

With continued reference to FIG. 2B, the cement composition 14 may bepumped down the interior of the casing 30. The cement composition 14 maybe allowed to flow down the interior of the casing 30 through the casingshoe 42 at the bottom of the casing 30 and up around the casing 30 intothe wellbore annulus 32. The cement composition 14 may be allowed to setin the wellbore annulus 32, for example, to form a cement sheath thatsupports and positions the casing 30 in the wellbore 22. While notillustrated, other techniques may also be utilized for introduction ofthe cement composition 14. By way of example, reverse circulationtechniques may be used that include introducing the cement composition14 into the subterranean formation 20 by way of the wellbore annulus 32instead of through the casing 30.

As it is introduced, the cement composition 14 may displace other fluids36, such as drilling fluids and/or spacer fluids that may be present inthe interior of the casing 30 and/or the wellbore annulus 32. At least aportion of the displaced fluids 36 may exit the wellbore annulus 32 viaa flow line 38 and be deposited, for example, in one or more retentionpits 40 (e.g., a mud pit), as shown on FIG. 2A. Referring again to FIG.2B, a bottom plug 44 may be introduced into the wellbore 22 ahead of thecement composition 14, for example, to separate the cement composition14 from the fluids 36 that may be inside the casing 30 prior tocementing. After the bottom plug 44 reaches the landing collar 46, adiaphragm or other suitable device ruptures to allow the cementcomposition 14 through the bottom plug 44. In FIG. 2B, the bottom plug44 is shown on the landing collar 46. In the illustrated embodiment, atop plug 48 may be introduced into the wellbore 22 behind the cementcomposition 14. The top plug 48 may separate the cement composition 14from a displacement fluid 50 and also push the cement composition 14through the bottom plug 44.

Examples

The present invention is exemplified by the following examples. Theexamples are not intended and should not be taken to limit, modify ordefine the scope of the present invention in any manner.

Six cement additive composition samples were prepared. The six sampleswere designated as Samples A-F and the composition of each is shown inTable 1, wherein the percentages are by weight of the total cementadditive composition. In the samples, two different formulations ofcalcium aluminate cement (CAC) were used. The CAC's were calciumaluminate cement made by Kerneos Inc. and marketed under the trade nameSecar 71 and Secar 51. Secar 51 contains more of the monocalciumaluminate clinker phase.

TABLE 1 Component Sample A Sample B Sample C Sample D Sample E Sample FCalcium Sulfate 71.4% 62.7% 60.2% 54.0% 71.4% 71.3% Secar 71 CAC 17.4%26.1% 28.9% 34.8% — 17.4% Secar 51 CAC — — — — 17.4% — Calcium Hydroxide10.0% 10.0% 9.6% 10.0% 10.0% 10.0% Sodium Bicarbonate 1.2% 1.2% 1.2%1.2% 1.2% 1.2% Lithium Carbonate 0.2% Total 100.0% 100.0% 100.0% 100.0%100.0% 100.0%

Seven cement slurry samples were then prepared comprising Class HPortland cement. The first cement sample designated as Sample I had noexpansion additive. The other six cement samples each contained one ofcement additive Samples A-F and were designated as cement Sample II.A,Sample II.B, Sample II.C, Sample II.D, Sample II.E and Sample II.F,respectively. All the samples included calcium chloride as a setaccelerator. Also, all the samples included a fluid loss additivemarketed under the trade name Halad 322 by Halliburton Energy Services,Inc. The formulations of the cement samples are shown in Table II,wherein the percentages are by weight of the Portland cement.

TABLE 2 Component Sample I Sample II.A through II.F Class H PortlandCement 100.0% 100.0% Expansion Additive — 10.0% Fluid Loss Additive 0.6%0.6% Set Accelerator 1.0% 1.0% Deionized H₂O 49.4% 49.4%

Sample I was tested to gauge the performance of Portland cement withoutany expansion additive. Expansion additives A-F were mixed into Portlandcement sample II at 10% by weight of Portland cement, as indicated inTable 1. Samples I and Samples II.A-II.F were prepared under standardAPI conditions, then poured into expansion molds to be cured over a 7day period at 55° F. (12.8° C.) in a recirculating water bath. Theexpansion measurements for each sample were taken daily with amicrometer. The results from the expansion tests are displayed in FIG.1.

All test samples that contained expansion additives showed greateroverall expansion than Portland cement alone, except Sample II.E. Theseresults indicate that increasing the amount of CAC provides greateroverall expansion when cured at 55° F. (12.8° C.). Sample II.D containedtwice the CAC as Sample II.A, and expanded nearly 130% more over the 7day period. Samples II.B and Sample II.C, which contained one and halftimes the amount of CAC in Sample II.A, showed only moderateimprovements in expansion.

Each of Samples II.A-II.E did not set in 24 hours, and thus, anexpansion reading could not be recorded at the end of day 1. Thesesamples were observed to have set within 48 hours, however, andmeasurements were taken from that point onward.

Sample II.F had the same formulation as Sample II.A but lithiumcarbonate was added as a component to the expansion additive. Lithiumcarbonate was added at 0.2% by weight of expansion additive composition.When cured in the water bath at 55° F. (12.8° C.), Sample II.F setsuitably and expanded a great deal within 24 hours. This represented asignificant improvement over the previously tested samples. The overallexpansion of Sample II.F was nearly 200% greater than expansion forSample II.A under the test conditions. Furthermore, the expansion ratein the early states of curing (i.e. within 3 days) and through theentire test period are greater for Sample II.F than any other sampletested. FIG. 2 charts the expansion rate for each test sample throughthe initial period (day 0-3) and over the entire test period (day 0-7).

As can be seen, the expansion additive containing the lithium ioncompound gives rapid expansion, even at low temperatures, and providesmuch improved overall expansion. The lithium compound additive iscapable of producing expansion in set cements when the temperature is ator below room temperature and minimizes the amount of calcium aluminatecement additive needed as illustrated by a comparison of Samples II.Dand II.F. Sample II.D has the closest performance to that of Sample II.Fbut utilizes twice the amount of CAC and does not achieve as good aresult in setting time and expansion.

In accordance with the above disclosure, in one embodiment there isprovided an expansion additive composition for use in Portland cement.The additive, comprises a calcium aluminate cement and lithium compound.The calcium aluminate cement is present in an amount from about 5% toabout 50% by weight of the composition, and the lithium compound in anamount from about 0.01% to about 5.00% by weight of the composition.More preferably, the calcium aluminate cement is in an amount from about10% to about 40% by weight of the composition, and the lithium compoundis in an amount from about 0.05% to about 1.00% by weight of thecomposition. Alternatively, the calcium aluminate cement is in an amountfrom 15% to 35% by weight of the composition, and the lithium compoundis in an amount from 0.10% to 0.50% by weight of the composition.

The lithium compound can be a lithium salt. The lithium salt can beselected from the group consisting of lithium carbonate, lithiumhalides, lithium sulfate, hydrates of lithium sulfate, lithium nitrate,lithium hydroxide, and mixtures thereof. Additionally, the compositioncan further comprise calcium sulfate present in an amount from about 50%to about 80% by weight of the composition. Also, the composition cancomprise calcium hydroxide present in an amount from about 1% to about20% by weight of the composition; and sodium bicarbonate present in anamount from about 0.1% to about 5.0% by weight of the composition.

In another aspect, the expansion additive composition for use inPortland cement consists essentially of: a calcium aluminate cement inan amount from about 5% to about 50% by weight of the composition; alithium compound in an amount from 0.01% to 5.00% by weight of thePortland cement; and one or more compounds selected from the groupconsisting of calcium sulfate, calcium hydroxide, sodium bicarbonate, aset accelerator, and a fluid loss additive.

In another embodiment, there is provided an expansive cement compositioncomprising a Portland cement, calcium aluminate cement, lithium compoundand calcium sulfate. The calcium aluminate cement can be present in anamount from about 0.5% to about 8.0% by weight of the Portland cement.The lithium compound can be present in an amount from about 0.001% toabout 0.500% by weight of said Portland cement. Preferably, the calciumaluminate cement can be present in an amount from about 1.0% to about5.0% by weight of the Portland cement and the lithium compound can bepresent in an amount from about 0.005% to about 0.150% by weight of thePortland cement. Alternatively, the calcium aluminate cement can bepresent in an amount from 1.5% to 3.5% by weight of the Portland cement,and the lithium compound can be in an amount from 0.010% to 0.100% byweight of the Portland cement. The cement composition can comprisecalcium sulfate present in an amount from about 1% to about 15% byweight of the Portland cement.

The cement composition can have, during and after setting, at least a10% increase in volume compared to the preset composition when settingoccurs at a temperature of below 100° F. (37.8° C.), at a temperaturebelow about 73° F. (23° C.), below 60° F. (15.6° C.) or at about 55° F.(12.8° C.) or below. Additionally, the increase in volume after settingcan be at least 15% when setting occurs at a temperature of below 100°F. (37.8° C.), at a temperature below about 73° F. (23° C.), below 60°F. (15.6° C.) or at about 55° F. (12.8° C.) or below. Also, the increasein volume after setting can be at least 17% when setting occurs at atemperature of below 100° F. (37.8° C.), at a temperature below about73° F. (23° C.), below 60° F. (15.6° C.) or at about 55° F. (12.8° C.)or below.

Also, the cement composition can comprise calcium hydroxide present inan amount from about 0.1% to about 3.0% by weight of said Portlandcement, and sodium bicarbonate present in an amount from about 0.01% toabout 1.00% by weight of the Portland cement. In some embodiments thecement composition comprises calcium chloride in an amount from about0.1% to about 5.0%, or from 0.5% to 2% by weight of the Portland cement.

In another aspect the expansive cement composition consists essentiallyof: a Portland cement; a fluid loss additive; a calcium aluminate cementin an amount from about 0.5% to about 8.0% by weight of the Portlandcement; a lithium compound in an amount from about 0.001% to about0.500% by weight of the Portland cement; calcium sulfate; water; and oneor more compound selected from the group consisting of calciumhydroxide, sodium bicarbonate, a set accelerator and a fluid lossadditive.

In a further embodiment, there is provided a method for cementing acasing in a bore of a well having a borehole wall, comprising placing acement slurry of one of the above described expansive cementcompositions between the casing and the borehole wall; wherein theborehole wall and the casing are at a temperature below about 100° F.(37.8° C.). Additionally, the borehole wall and the casing can be at atemperature below about 73° F. (23° C.). In some embodiments, theborehole wall and the casing can be below 60° F. (15.6° C.) or they canbe at about 55° F. (12.8° C.) or below.

Therefore, the present invention is well adapted to attain the ends andadvantages mentioned, as well as those that are inherent therein. Theparticular embodiments disclosed above are illustrative only, as thepresent invention may be modified and practiced in different butequivalent manners apparent to those skilled in the art having thebenefit of the teachings herein. Furthermore, no limitations areintended to the details of construction or design herein shown, otherthan as described in the claims below. It is therefore evident that theparticular illustrative embodiments disclosed above may be altered ormodified, and all such variations are considered within the scope andspirit of the present invention. While compositions and methods aredescribed in terms of “comprising,” “containing,” “having,” or“including” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsand steps. Whenever a numerical range with a lower limit and an upperlimit is disclosed, any number and any included range falling within therange are specifically disclosed. In particular, every range of values(of the form, “from about a to about b,” or, equivalently, “fromapproximately a to b,” or, equivalently, “from approximately a-b”)disclosed herein is to be understood to set forth every number and rangeencompassed within the broader range of values. Also, the terms in theclaims have their plain, ordinary meaning unless otherwise explicitlyand clearly defined by the patentee.

What is claimed is:
 1. An expansion additive composition for use inPortland cements comprising: a calcium aluminate cement in an amountfrom about 5% to about 50% by weight of the composition; a lithiumcompound in an amount from about 0.01% to about 5.00% by weight of thecomposition; calcium hydroxide present in an amount from about 1% toabout 20% by weight of the composition; and sodium bicarbonate presentin an amount from about 0.1% to about 5.0% by weight of the composition.2. The composition of claim 1, further comprising calcium sulfatepresent in an amount from about 50% to about 80% by weight of thecomposition.
 3. The composition of claim 1, wherein said calciumaluminate cement is in an amount from about 10% to about 40% by weightof the composition and wherein said lithium compound is in an amountfrom about 0.05% to about 1.00% by weight of the composition.
 4. Thecomposition of claim 3, wherein said calcium aluminate cement is in anamount from 15% to 35% by weight of the composition and wherein saidlithium compound is in an amount from 0.10% to 0.50% by weight of thecomposition.
 5. The composition of claim 1, wherein said lithiumcompound is a lithium salt selected from the group consisting of lithiumcarbonate, lithium halides, lithium sulfate, hydrates of lithiumsulfate, lithium nitrate, lithium hydroxide, and mixtures thereof. 6.The composition of claim 1, further comprising calcium sulfate, andwherein: said calcium aluminate cement is in an amount from 15% to 35%by weight of the composition; said lithium compound is a lithium saltselected from the group consisting of lithium carbonate, lithiumhalides, lithium sulfate, hydrates of lithium sulfate, lithium nitrate,lithium hydroxide, and mixtures thereof, and said lithium salt is in anamount from 0.10% to 0.50% by weight of the composition; said calciumsulfate is present in an amount from about 50% to about 80% by weight ofthe composition.
 7. A method of using an expansion additive composition,the method comprising: mixing an additive composition, a Portland cementand water so as to form a slurry, wherein the additive compositioncomprises: a calcium aluminate cement in an amount from about 0.5% toabout 8.0% by weight of said Portland cement; a lithium compound in anamount from about 0.001% to about 0.50% by weight of said Portlandcement; calcium sulfate present in an amount from about 1% to about 15%by weight of said Portland cement; calcium hydroxide present in anamount from about 0.1% to about 3.0% by weight of said Portland cement;and sodium bicarbonate present in an amount from about 0.01% to about1.00% by weight of said Portland cement; and introducing the slurry intoa subterranean formation.
 8. The method of claim 7, wherein saidsubterranean formation is at a temperature below about 100° F.
 9. Themethod of claim 8, wherein said composition results in a 10% increase involume of the slurry when setting occurs at a temperature of below 100°F. (37.8° C.).
 10. The method of claim 9, wherein said subterraneanformation is at a temperature below about 73° F. (23° C.).
 11. Themethod of claim 7, wherein a bore of a well extends through saidsubterranean formation and the method further comprises allowing theslurry to form a plug in the bore.
 12. The composition of claim 7,wherein the lithium compound is a lithium salt selected from the groupconsisting of lithium carbonate, lithium halides, lithium sulfate,hydrates of lithium sulfate, lithium nitrate, lithium hydroxide, andmixtures thereof.
 13. The method of claim 12, wherein said calciumaluminate cement is in an amount from about 1.0% to about 5.0% by weightof said Portland Cement, and wherein said lithium compound is in anamount from about 0.005% to about 0.150% by weight of said Portlandcement.
 14. The method of claim 13, wherein said calcium aluminatecement is in an amount from 1.5% to 3.5% by weight of said Portlandcement and said lithium compound is in an amount from 0.010% to 0.100%by weight of said Portland cement.
 15. The method of claim 14, whereinsaid composition results in at least a 17% increase in volume of theslurry when setting occurs at a temperature of below 60° F. (15.6° C.).16. The method of claim 15, wherein a bore of a well extends throughsaid subterranean formation with said bore defined by a borehole wall,wherein a casing is in said bore, and wherein the method furthercomprises: placing the slurry between the casing and the borehole wall.17. The method of claim 16, further comprising allowing the slurry toform a plug in the bore.
 18. The method of claim 7, wherein saidadditive composition, said Portland cement and water are mixed usingmixing equipment.
 19. The method of claim 7, wherein the slurry isintroduced into the subterranean formation using one or more pumps. 20.A method of using an expansion additive composition, the methodcomprising: mixing an additive composition, a Portland cement and waterso as to form a slurry, wherein the additive composition comprises: acalcium aluminate cement in an amount from about 1.0% to about 5.0% byweight of said Portland cement; a lithium salt in an amount from about0.005% to about 0.150% by weight of said Portland cement, wherein thelithium salt is selected from the group consisting of lithium carbonate,lithium halides, lithium sulfate, hydrates of lithium sulfate, lithiumnitrate, lithium hydroxide, and mixtures thereof; calcium sulfatepresent in an amount from about 1% to about 15% by weight of saidPortland cement; calcium hydroxide present in an amount from about 0.1%to about 3.0% by weight of said Portland cement; and sodium bicarbonatepresent in an amount from about 0.01% to about 1.00% by weight of saidPortland cement; and introducing the slurry into an annulus between acasing and a borehole wall, wherein said borehole wall and said casingare at a temperature below about 100° F., and wherein said compositionresults in a 10% increase in volume of the slurry when setting occurs ata temperature of below 100° F. (37.8° C.).